NOTES
Nov.. 1950
5315
The 3,5-dinitrobenzoate melted at 88-90 '* (92 -) after one crystallizationfrom ethanol. When the hydrogenation was attempted in aqueous suspension, no reduction took place and 90% of the dioxane was recovered unchanged. 3-Phenyl-1-butanol was prepared similarly by the hydrogenation of 175 g. of 4-methyl-4-phenyl-l,3-dioxane in the presence of 13 g. of copper chromite at 225-230" and 800-1600 p.s.i. Distillation yielded 100 g. (68%) of 3; phenyl-1-butanol, b. p. 121-123" (13 mm.) (125.5-128.0 at 13 mm.),* TPD 1.5165.
exception of the 4-hydroxy-2-methylbenzopteridine described among the alloxazines by Gowenlock, Newbold and Spring.2 Compounds of this type were considered to be of some biological interest because of the analogous structure which exists in thiamine. The 4,5-diamino-6-hydroxy2-methylpyrimidine and 2-methyl-4,5,6-triaminopyrimidine, prepared according to the methods described in the l i t e r a t ~ r e ,were ~ used for the condensation with glyoxal bisulfite and oxalic (6) Melting point uncorrected. (7) Shriner and Fuson, "Systematic Identification of Organic acid. Both 4,5-diamino-6-hydroxy-2-methylCompounds," John Wiley and Sons, Inc., New York, N. Y., 1948, p. pyrimidine and 2-methyl-4,5,6-triaminopyrimidinc 227. condensed satisfactorily with oxalic acid, but (8) Rupe and Walraven. Hclo. Chim. Acta, 18, 361 (1930). with glyoxal bisulfite the former gave a product MONSANTO CHEMICAL Co. which could not be obtained in a satisfactory state CENTRAL RESEARCH DEPT. RECEIVED MAY27, 1950 of purity while the latter failed to yield a solid DAYTON 7, OHIO product. These difficulties of condensation are not unusual in working with pyrimidines, as On the Kolbe-Schmitt Reaction reported by Kuhn and Cook.4 BY LLOYD N. FERGUSON,~ RICHARDR. HOLMES*AND Table I lists the pteridines prepared together MELVINCALVIN with their ultraviolet absorption spectra in alkaThe recent publication of Cameron, Jeskey line solution. Also, their solubility in phosphate and Baine3 on the Kolbe-Schmitt reaction has buffer is given. It was observed that the inprompted us to report an interesting observation troduction of the methyl group in 2-position from an investigation which included the use of considerably increased the solubility of the pterithis reaction. At that time, it was desired to dines. The paper chromatographic analysis of solution of the 2-methyl carbonate o-substituted phenols in the second the 0.5 N "*OH ortho position. In view of the fact that potas- substituted pteridines gave a bright blue fluoressium salts give higher percentages of the para acids cence. The pyrimidine precursors upon paper in this r e a ~ t i o na, ~lithium salt was tried, following chromatography not only differed in their Rf a suggestion of Dr. R. H. Bailes. It is noteworthy values, but did not show any appreciable fluoresthat, under the conditions previously reported for cence. TABLEI the carbonation of sodium o-fluorophenoxide,6 only the ortho acid was obtained from lithium oRI fluorophenoxide. In general, only about 30% of THE2-METHYLPTERIDINE the lithium salt was carbonated, and the yields RING of acid ranged between 65 and 70%, based on unrecovered fluorophenol. On the other hand, potassium o-fluorophenoxide yielded the ortho and Soly. in para acids in a 1:3 mole ratio. Thus, under comU.V. spectra in 0.1 N phosphate NaOH buffer a t parable conditions, there is a decreasing trend in (PH 8.55-9.0) pH 7.4. the molar ratios of ortho:para acids of 1:0 from ComMax. mg./100 pound RI RI Ra A. Min. ml. the lithium salt, 3 :2 from the sodium salt and 1:3 I OH OH OH 3460 3070 5 from the potassium salt. 2940 2690 (1) Howard University, Washington, D. C. (2) Graduate School, University of Minnesota, Minneapolis, Minn. (3) D. Cameron, H. Jeskey and 0. Baine, J . Org. Chcm., 16, 233 (1949). (4) H. Kolbe, J . prakl. Chcm., [2] 10, 100 (1874). JOURNAL, 68, (5) L. N. Ferguson, J. C. Reid and M. Calvin, THIS 2502 (1946).
DEPARTMENT OF CHEMISTRY UNIVERSITY OF CALIFORNIA BERKELEY. CALIF. RECEIVED JULY 20, 1950
Pteridine Studies. 11. 2-Methylpteridines BY EMERYM. GAL^
A search of the literature revealed no reports on 2-methyl substituted pteridines with the (1) U.S. Public H d t h Spedal Fellow. This work w w supported by a grant from t h e Cancer R-h Ocrnta Prnnch, U. 0, Public H r l t h B a i w to P. Y. Omnbrii.
I1
NHI
OH
OH
4,5-Diamino-6hydroxy-2-methylpyrimidine (b) 2-Methyl-4,5.6-triaminopyrimidine
2420 3325 2275
2300 3226 shoulder 2670 2400 shoulder
2730
2345
2750
2390
40
(a)
Experimental
2-Methyl-4,6,7-trihydroxppyrimido-(4,5-b)-pyrazine (I).*ne gram of 4,5-diamino-6-hydroxy-2-methylpynmidine bisuliite, 1.0 g. of sodium oxalate and 5.0 g. of anhydrous oxalic acid were thoroughly mixed and then heated in a container under vacuum, gradually bringing the temperature up to 250'. After three hours of heating the dark brown solid was dissolved in 150 ml. of 2 N (2) Gowenlock, Newbold and Spring, 3. Ckm. Soc., 617 (1948). (8) Lythgoe, Todd and Tophm, Wd.. 816 (1944h (4) Puhn and Cook, k., TO, 761 (1937).
